US3859348A - Method of forming glyoxylic acid semicarbazone - Google Patents
Method of forming glyoxylic acid semicarbazone Download PDFInfo
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- US3859348A US3859348A US405833A US40583373A US3859348A US 3859348 A US3859348 A US 3859348A US 405833 A US405833 A US 405833A US 40583373 A US40583373 A US 40583373A US 3859348 A US3859348 A US 3859348A
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- Prior art keywords
- acid
- cyanate
- hydrazine
- solution
- glyoxylic acid
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 25
- QZSYGBNBQHRGKK-ORCRQEGFSA-N (2e)-2-(carbamoylhydrazinylidene)acetic acid Chemical compound NC(=O)N\N=C\C(O)=O QZSYGBNBQHRGKK-ORCRQEGFSA-N 0.000 title description 10
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 40
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims abstract description 14
- 150000007659 semicarbazones Chemical class 0.000 claims abstract description 12
- HFFLGKNGCAIQMO-UHFFFAOYSA-N trichloroacetaldehyde Chemical compound ClC(Cl)(Cl)C=O HFFLGKNGCAIQMO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims description 19
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- GKKCIDNWFBPDBW-UHFFFAOYSA-M potassium cyanate Chemical group [K]OC#N GKKCIDNWFBPDBW-UHFFFAOYSA-M 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000011874 heated mixture Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 abstract description 22
- 239000007787 solid Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- 239000002244 precipitate Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- SSPYSWLZOPCOLO-UHFFFAOYSA-N 6-azauracil Chemical compound O=C1C=NNC(=O)N1 SSPYSWLZOPCOLO-UHFFFAOYSA-N 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- UJTTUOLQLCQZEA-UHFFFAOYSA-N 9h-fluoren-9-ylmethyl n-(4-hydroxybutyl)carbamate Chemical compound C1=CC=C2C(COC(=O)NCCCCO)C3=CC=CC=C3C2=C1 UJTTUOLQLCQZEA-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- -1 alkali metal cyanates Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000001174 ascending effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 238000010420 art technique Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229940126534 drug product Drugs 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- MOOYVEVEDVVKGD-UHFFFAOYSA-N oxaldehydic acid;hydrate Chemical compound O.OC(=O)C=O MOOYVEVEDVVKGD-UHFFFAOYSA-N 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C281/00—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
- C07C281/06—Compounds containing any of the groups, e.g. semicarbazides
- C07C281/08—Compounds containing any of the groups, e.g. semicarbazides the other nitrogen atom being further doubly-bound to a carbon atom, e.g. semicarbazones
- C07C281/10—Compounds containing any of the groups, e.g. semicarbazides the other nitrogen atom being further doubly-bound to a carbon atom, e.g. semicarbazones the carbon atom being further bound to an acyclic carbon atom or to a carbon atom of a ring other than a six-membered aromatic ring
Definitions
- 6- azauracil comprises the cyclization of glyoxylic acid semicarbazone.
- this semicarbazone is a valuable starting material in the synthesis of 6-azauracil which in turn is utilized to form valuable drug products through additional reactions.
- glyoxylic acid semicarbazone involves. the reaction of glyoxylic acid and semicarbazide. Glyoxylic acid is relatively expensive and thus the cost of the desired semicarbazone is quite expensive. Another reported method for forming a semicarbazone is by heating chloral and semicarbazide hydrochloride in an aqueous solution. Once again, in this instance, the semicarbazide hydrochloride is an expensive starting material and thus serves to add sub stantially to the cost of the semicarbazone to be formed. It should be apparent that if the semicarbazone is expensive as a starting material for forming the 6- azauracil then the price of the resulting products, or drugs produced, will reflect same. A reduction in the cost of any intermediate or starting material in the formation of such products is valuable in making the resulting item more economically feasible.
- the herein invention comprises a new method forpreparing glyoxylic acid semicarbazone utilizing inexpensive ingredients such that the resulting semicarbazone will have a reduced price as compared to that manufactured in prior art technique.
- potassium cyanate is reacted with a neutralized hydrazine solution for a period of several hours.
- the solution is then reacted with either glyoxylic acid or chloral.
- chloral is used, the pH of the solution is adjusted prior to addition of the chloral.
- a precipitate of the semicarbazone is formed from the reactions. It is believed that the invention will be further understood from the following description and examples.
- a neutral aqueous solution of hydrazine is first prepared.
- the amount of hydrazine in the solution can range from I to 30 weight percent. It is generally preferred that the solution contain about 10 percent hydrazine.
- Added to the neutral hydrazine solution is a cyanate.
- cyanate Preferably, potassium cyanate is utilized.
- Other alkali metal cyanates are somewhat unstable in water, particularly potassium cyanate, it is desirable to have a small excess over that stoichiometrically required for the reaction involved. Thus, it is preferable to 'have from 5-25 weight percent excess of the cyanate.
- the third additional ingredient initially added to the reaction is an acid.
- hydrochloric acid is preferred, other mineral acids, such as sulfuric and phosphoric acids can be utilized. Additionally, weak acids are contemplated such as acetic and formic acid, though they are not as preferred. The acid could be any convenient strength or concentration. However, there must be at least one mole equivalent of acid for each mole of cyanate utilized, as can bereadily apparent from the following equation between the three reactants to form the semicarbazide.
- the above reaction 1 forms, as can be seen, an intermediate semicarbazide in solution.
- one of the advantages of the herein invention is to utilize a solution of the semicarbazide formed in reaction 1 above without the need for isolating the semicarbazide prior to forming the desired product.
- the above reac- 2 tion to form the intermediate semicarbazide can be carried out from 4 to 24 hours at room temperature. It has generally been found that 'the reaction is completed in eight hours. The completion of the reaction is dependent on temperature, time and concentration of reactants. The time of reaction can be reduce significantly by raising the temperature of the reaction to within the range of 50 to C, but reaction temperatures between 10 and C may be used.
- reaction labove can then be utilized in one of two ways, in accord with the herein invention.
- glyoxylic acid is added tothe mixture in an amount to stoichiometrically react with the semicarbazide. Once the acid is dissolved in solution, a new precipitate starts to form almost at once. The reaction is complete when no more precipitate forms which is in the range of from 15 minutes to 2 hours. The precipitate which crystallizes out, is the desired glyoxylic acid semicarbazone.
- the temperature of the reaction with the glyoxylic acid can vary from room temperature to near the boiling point of water. After the reaction, the mixture'should be cooled to at least room temperature to ensure a good yield.
- the reaction with the glyoxylic acid to form the desired semicarbazone is seen from reaction 2 below.
- the solution of the intermediate semicarbazide of reaction 1 is treated with further acid to bring the pH within the range of 5 to 7. This step of acid addition is preferred in order to assure that the further reaction required to form the desired semicarbazone will achieve a good yield of a pure material.
- the acidified solution is preferably cooled to room temperature before the next step which is extremely exothermic. After cooling to room temperature, chloral is then added in a stoichiometric amount equivalent to semicarbazide present.
- the melting point of the product was 207209 C compared with 207209 C for a known sample.
- Thin layer chromatography using Silufol UV 254 ascending in Butanol: Acetic Acid: Water, 812:2 gave a single spot indistinguishable from a known sample and with an R,
- EXAMPLE Il utes and a precipitate started forming. After atotal of 28 minutes, the reaction mixture was cooled in an ice bath for 20 minutes and then the precipitatewas collected, washed with cold water, methanol and air dried. Yield, 7.0 gms. of first-crop material. A second crop,
- the main cro'p had a melting point of 205-207 C compared to 207209 for a standard sample.
- a method of forming glyoxylic acid semicarbazone comprising:
- an alkali metal cyanate an aqueous neutral hydrazine solution having a concentration of hydrazine of from 1 to 30 weight per cent,said cyanate being present in an amount of about 5 to 25 weight percent excess of an equal molar amount of said hydrazine and at least one mole of an acid for each mole of said cyanate, reacting the mixture atfrom 10 to 80 C to form an intermediate semicarbazide in solution,
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method of forming glyoxylic acid semicarbozone by reacting a cyanate with a neutralized hydrazine solution for a period of time, followed by either addition of glyoxylic acid or adjusting the pH and adding chloral whereby a solid semicarbazone product is precipitated.
Description
United States Patent I191 Deutsch 1 Jan. 7, 1975 METHOD OF FORMING GLYOXYLIC ACID SEMI-CARBAZONE [52] LES. Cl. 260/534 R, 260/554 [51] Int. Cl C07c 133/04 [58] Field of Search 260/534 R, 554
[56] References Cited UNITED STATES PATENTS 2,779,786 1/1957 Coleman et a] 260/534 R 3,427,306 2/1969 Portelli 260/534 R Primary Examiner-Vivian Garner [57] ABSTRACT A method of forming glyoxylic acid semicarbozone by reacting a cyanate with a neutralized hydrazine solution for a period of time, followed by either addition of glyoxylic acid or adjusting the pH and adding chloral whereby a solid semicarbazone product is precipitatedi 8 Claims, N0 Drawings METHOD OF FORMING GLYOXYLlC ACID SEMl-CARBAZONE in the prior art for formulating the starting 6 azauracil.
Perhaps the most effective process for forming 6- azauracil comprises the cyclization of glyoxylic acid semicarbazone. Thus, this semicarbazone is a valuable starting material in the synthesis of 6-azauracil which in turn is utilized to form valuable drug products through additional reactions.
One obvious method of forming glyoxylic acid semicarbazone involves. the reaction of glyoxylic acid and semicarbazide. Glyoxylic acid is relatively expensive and thus the cost of the desired semicarbazone is quite expensive. Another reported method for forming a semicarbazone is by heating chloral and semicarbazide hydrochloride in an aqueous solution. Once again, in this instance, the semicarbazide hydrochloride is an expensive starting material and thus serves to add sub stantially to the cost of the semicarbazone to be formed. It should be apparent that if the semicarbazone is expensive as a starting material for forming the 6- azauracil then the price of the resulting products, or drugs produced, will reflect same. A reduction in the cost of any intermediate or starting material in the formation of such products is valuable in making the resulting item more economically feasible.
Briefly, the herein invention comprises a new method forpreparing glyoxylic acid semicarbazone utilizing inexpensive ingredients such that the resulting semicarbazone will have a reduced price as compared to that manufactured in prior art technique. In accord with the herein process, potassium cyanate is reacted with a neutralized hydrazine solution for a period of several hours. The solution is then reacted with either glyoxylic acid or chloral. When chloral is used, the pH of the solution is adjusted prior to addition of the chloral. In both instances, a precipitate of the semicarbazone is formed from the reactions. It is believed that the invention will be further understood from the following description and examples.
To form the glyoxylic acid semicarbazone, a neutral aqueous solution of hydrazine is first prepared. The amount of hydrazine in the solution can range from I to 30 weight percent. It is generally preferred that the solution contain about 10 percent hydrazine. Added to the neutral hydrazine solution is a cyanate. Preferably, potassium cyanate is utilized. Other alkali metal cyanates are somewhat unstable in water, particularly potassium cyanate, it is desirable to have a small excess over that stoichiometrically required for the reaction involved. Thus, it is preferable to 'have from 5-25 weight percent excess of the cyanate. The third additional ingredient initially added to the reaction is an acid. Though hydrochloric acid is preferred, other mineral acids, such as sulfuric and phosphoric acids can be utilized. Additionally, weak acids are contemplated such as acetic and formic acid, though they are not as preferred. The acid could be any convenient strength or concentration. However, there must be at least one mole equivalent of acid for each mole of cyanate utilized, as can bereadily apparent from the following equation between the three reactants to form the semicarbazide.
The above reaction 1 forms, as can be seen, an intermediate semicarbazide in solution. As will be seen, one of the advantages of the herein invention is to utilize a solution of the semicarbazide formed in reaction 1 above without the need for isolating the semicarbazide prior to forming the desired product. The above reac- 2 tion to form the intermediate semicarbazide can be carried out from 4 to 24 hours at room temperature. It has generally been found that 'the reaction is completed in eight hours. The completion of the reaction is dependent on temperature, time and concentration of reactants. The time of reaction can be reduce significantly by raising the temperature of the reaction to within the range of 50 to C, but reaction temperatures between 10 and C may be used.
The solution formed in reaction labove can then be utilized in one of two ways, in accord with the herein invention. In a first approach, glyoxylic acid is added tothe mixture in an amount to stoichiometrically react with the semicarbazide. Once the acid is dissolved in solution, a new precipitate starts to form almost at once. The reaction is complete when no more precipitate forms which is in the range of from 15 minutes to 2 hours. The precipitate which crystallizes out, is the desired glyoxylic acid semicarbazone. The temperature of the reaction with the glyoxylic acid can vary from room temperature to near the boiling point of water. After the reaction, the mixture'should be cooled to at least room temperature to ensure a good yield. The reaction with the glyoxylic acid to form the desired semicarbazone is seen from reaction 2 below.
The second approach utilizing the solution formed in reaction 1 above, eliminates the requirement for glyoxylic acid which is a relatively expensive ingredient. In this method, the solution of the intermediate semicarbazide of reaction 1 is treated with further acid to bring the pH within the range of 5 to 7. This step of acid addition is preferred in order to assure that the further reaction required to form the desired semicarbazone will achieve a good yield of a pure material. The acidified solution is preferably cooled to room temperature before the next step which is extremely exothermic. After cooling to room temperature, chloral is then added in a stoichiometric amount equivalent to semicarbazide present.
The mixture is then stirred as it is initially in two phases, and heated'with a bath set in a range of 7090 C EXAMPLE 1 Into a 125ml. Erlenmeyer flask was placed 2.9 mls. of 54.4% aqueous hydrazine solution, 50 mls. of water, 4.2 mls. of 12 N hydrocholoric acid, and last, 4.9 gms. of practical grade potassium cyanate. A'clear solution was obtained. The solution was allowed to stand at room temperature for 1 4 hours, and then 46 gms. of glyoxylic acid monohydrate was added. The acid quickly dissolved and a new precipitate started forming almost at once. After standing for 30 minutes, the precipitate was collected and washed with approximately 60 mls. of water. The solid was air dried to yield'5.0 gms. of white product which was glyoxylic acid semicarbazone.
The melting point of the product was 207209 C compared with 207209 C for a known sample. Thin layer chromatography using Silufol UV 254 ascending in Butanol: Acetic Acid: Water, 812:2 gave a single spot indistinguishable from a known sample and with an R,
EXAMPLE Il utes and a precipitate started forming. After atotal of 28 minutes, the reaction mixture was cooled in an ice bath for 20 minutes and then the precipitatewas collected, washed with cold water, methanol and air dried. Yield, 7.0 gms. of first-crop material. A second crop,
0.6 gms. formed in the mother liquors on standing overnight.
The main cro'p had a melting point of 205-207 C compared to 207209 for a standard sample. Thin layer chromatography using Silufol UV 254. ascending in ButanolzAcetic Acid:Water, 8:2:2 gave a single spot of R, 0.60 indistinguishable from that of a known sample.
I claim: l. A method of forming glyoxylic acid semicarbazone comprising:
mixing an alkali metal cyanate, an aqueous neutral hydrazine solution having a concentration of hydrazine of from 1 to 30 weight per cent,said cyanate being present in an amount of about 5 to 25 weight percent excess of an equal molar amount of said hydrazine and at least one mole of an acid for each mole of said cyanate, reacting the mixture atfrom 10 to 80 C to form an intermediate semicarbazide in solution,
adding an acid to said intermediate semicarbazide solution in an amount sufficient to bring the pH within the range of 5 to 7, and heating the mixture at from 70-90 C., under reflux conditions after the chloral has been added.
2. The method of claim 1 further including the step of cooling said heated mixture after about 30 minutes of heating. I
3. The method of claim 2 whereinsaid cooling is to below room temperature and the reaction mixture maintained in a cooled condition for at least about 30 minutes. 7 t
4. The method of claim 1 wherein said cyanate is potassium cyanate.
5. The method ofclaim 1 wherein said aqueous neutral hydrazine solution has a concentration of about 10 per cent by weight hydrazine. g
6. The method of claim 1 wherein said cyanate and hydrazine are reacted at a temperature of from about 50 C to about 70 C.
chloric acid.
Claims (8)
1. A METHOD OF FORMING GLYOXLIC ACID SEMICARBAZONE COMPRISING: MIXING AN ALKALI METAL CYANATE, AN AQUEOUS NEUTRAL HYDRAZINE SOLUTION HAVING CONCENTRATION OF HYDRAZINE OF FROM 1 TO 30 WEIGHT PER CENT, SAID CYANATE BEING PRESENT IN AN AMOUNT OF ABOUT 5 TO 25 WEIGHT PER CENT EXCESS OF AN EQUAL MOLAR AMOUNT OF SAID HYDRAZINE AND AT LEAST ONE MOLE OF AN ACID FOR EACH MOLE OF SAID CYANATE, REACTING THE MIXTURE AT FROM 10* TO 80*C TO FORM AN INTERMEDIATE SEMICARBAZIDE IN SOLUTION, ADDING AN ACID TO SAID INTERMEDIATE SEMICARBAZIDE SOLUTION IN AN AMOUNT SUFFICIENT TO BRING THE PH WITHIN THE RANGE OF 5 TO 7, AND HEATING THE MIXTURE AT FROM 70*-90*C., UNDER REFLUX CONDITIONS AFTER THE CHLORAL HAS BEEN ADDED.
2. The method of claim 1 further including the step of cooling said heated mixture after about 30 minutes of heating.
3. The method of claim 2 wherein said cooling is to below room temperature and the reaction mixture maintained in a cooled condition for at least about 30 minutes.
4. The method of claim 1 wherein said cyanate is potassium cyanate.
5. The method of claim 1 wherein said aqueous neutral hydrazine solution has a concentration of about 10 per cent by weight hydrazine.
6. The method of claim 1 wherein said cyanate and hydrazine are reacted at a temperature of from about 50* C to about 70* C.
7. The method of claim 1 wherein said acid is selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid and formic acid.
8. The method of claim 7 wherein said acid is hydrochloric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US405833A US3859348A (en) | 1972-06-08 | 1973-10-12 | Method of forming glyoxylic acid semicarbazone |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US261025A US3859347A (en) | 1972-06-08 | 1972-06-08 | Method of forming glyoxylic acid semicarbazone |
| US405833A US3859348A (en) | 1972-06-08 | 1973-10-12 | Method of forming glyoxylic acid semicarbazone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3859348A true US3859348A (en) | 1975-01-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US405833A Expired - Lifetime US3859348A (en) | 1972-06-08 | 1973-10-12 | Method of forming glyoxylic acid semicarbazone |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2779786A (en) * | 1953-04-17 | 1957-01-29 | Norwich Pharma Co | Process of preparing 2-semicarbazidoacetic acid |
| US3427306A (en) * | 1965-08-13 | 1969-02-11 | Zambon Spa Bresso | Process for the manufacture of n-(5 - nitro - 2 - furfuryliden) - 1 - amino-hydantoin |
-
1973
- 1973-10-12 US US405833A patent/US3859348A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2779786A (en) * | 1953-04-17 | 1957-01-29 | Norwich Pharma Co | Process of preparing 2-semicarbazidoacetic acid |
| US3427306A (en) * | 1965-08-13 | 1969-02-11 | Zambon Spa Bresso | Process for the manufacture of n-(5 - nitro - 2 - furfuryliden) - 1 - amino-hydantoin |
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